Phosphino derivatives

Abstract

The reaction of compounds of the formula: X.sub.2 O.sub.3 P CHY CZ.sub.2 where Y and each Z are each H, PO 3 X 2 , SO 3 X or CO 2 X (e.g. vinyl phosphonic acid or vinylidene diphosphonic acid) with hypophosphorous acid in the presence of free radicals provides novel compounds X 2 O 3 PCHYCZ 2 PO 2 XH which react with monomers such as vinyl sulphonate, vinyl phosphonate, vinylidene diphosphonate and acrylic acid to form telomers useful for scale inhibition, especially barium scale in oil wells. The polymers show better absorption to rock than PVSA and better thermal stability than random copolymers containing equivalent phosphorus.

What is claimed is: 
     
       1. A composition having the formula:   X.sub.2 O.sub.3 P.CHYCZ.sub.2 PO.sub.2 XR                  (I)     where X is selected from the group consisting of H, alkali metal, alkaline earth or other polyvalent metal, ammonium and organic bases capable of forming a water-soluble salt of said compound, and R is selected from the group consisting of hydrogen, a diphosphonoethyl group and a homo- or co- polymeric chain comprising between 1 and 100,000 groups, said groups being derived from at least one unsaturated compound in which the multiple bond is activated chemically by an adjacent electron withdrawing group, and Y and each Z are individually selected from the group consisting of hydrogen, a PO 3  X 2 , SO 3  X, CO 2  X, an alkyl moiety and an aryl moiety.   
     
     
       2. A composition according to claim 1, wherein X is selected from the group consisting of H, alkali metal and ammonia, Y is H, each Z is H, and R is H. 
     
     
       3. A composition according to claim 1, wherein X is selected from the group consisting of H, alkali metal and ammonia, Y is X 2  O 3  P--, each Z is H and R is H. 
     
     
       4. A composition according to claim 1, wherein X is selected from the group consisting of H, an alkali metal and ammonia, Y is H or X 2  O 3  O--, each Z is H and R is --CH 2  CYPO 3  X 2 . 
     
     
       5. A composition according to claim 1, which is a telomer wherein R is a homopolymeric or copolymeric chain and said unsaturated compound in which the multiple bond is activated chemically by an adjacent electron-withdrawing group consists of at least one monomer selected from the group consisting of unsaturated sulphonic acids, phosphonic acids, carboxylic acids, vinyl alcohol, vinyl chloride, vinyl acetate and their water soluble salts. 
     
     
       6. A composition according to claim 5, which is a telomer wherein said monomer comprises at least one member of the group consisting of vinyl sulphonic acid and its water soluble salts. 
     
     
       7. A composition according to claim 5 wherein said monomer comprises at least one of vinyl phosphonic acid and its water soluble salts. 
     
     
       8. A composition according to claim 5 wherein said monomer comprises at least one of vinylidene diphosphonic acid and its water soluble salts. 
     
     
       9. A composition according to claim 5 wherein said monomer comprises acrylic acid. 
     
     
       10. A composition according to claim 9, wherein said monomer additionally comprises at least one monomer selected from the group consisting of vinyl phosphonic acid, vinylidene diphosphonic acid and their salts. 
     
     
       11. A composition according to claim 5, wherein the monomer comprises at least one member selected from the group consisting of methacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, vinyl alcohol, vinyl chloride, vinyl acetate, styrene sulphonic acid, 2-acrylamido-2- methylpropane sulphonic acid and their water soluble salts and from 0 to 4 members selected from the group consisting of vinyl sulphonic acid, vinyl phosphonic acid, vinylidene diphosphonic acid, acrylic acid and their salts. 
     
     
       12. A composition according to claim 4 or claim 5 which is a water insoluble polyvalent metal salt. 
     
     
       13. A composition according to claim 12, wherein said polyvalent metal is selected from the group consisting of calcium, barium, strontium, zinc, magnesium, aluminum, nickel, copper, cobalt and iron. 
     
     
       14. A method of manufacture of a composition according to claim 2 which comprises reacting vinyl phosphonic acid or a salt thereof with hypophosphorous acid or a salt thereof in aqueous solution in the presence of a source of free radicals. 
     
     
       15. A method of manufacture of a telomer which comprises reacting a water soluble compound according to claim 2 with more than 1 molar proportion of an unsaturated compound having an ethylenic or acetylenic bond activated by an adjacent sulphonate, phosphonate or carboxylate group, in aqueous solution in the presence of a free radical source. 
     
     
       16. A method of inhibiting scale formation in an aqueous system which is prone to scale formation, which comprises adding to the system a scale inhibiting amount of a composition according to claim 4 or claim 5. 
     
     
       17. A method of inhibiting scale formation according to claim 16 wherein said system comprises an oil well and means for injecting water into the oil bearing strata. 
     
     
       18. A method according to claim 17, wherein said scale comprises at least one of barium sulphate and barium carbonate. 
     
     
       19. A method of inhibiting corrosion of metal surfaces by aqueous systems having a tendency to cause such corrosion, which comprises adding a corrosion inhabiting amount of a composition according to either claim 4 or 5 to said aqueous systems. 
     
     
       20. A method according to claim 16, wherein said composition is used in a concentration of from 0.1 to 200 ppm. 
     
     
       21. A method according to claim 20 wherein said concentration is form 1.5 to 20 ppm. 
     
     
       22. A corrosion inhibiting coating composition comprising as a pigment, a salt according to claim 12. 
     
     
       23. A coating composition according to claim 22 comprising a volatile liquid vehicle and/or a drying oil. 
     
     
       24. A method of forming a corrosion inhibitory coating on metal surfaces which comprises contacting said surfaces with an aqueous solution of a composition according to claim 1, which is a water soluble salt. 
     
     
       25. A method according to claim 24 wherein said water soluble salt is used in a concentration of from 10 to 500 ppm. 
     
     
       26. A detergent composition comprising a surfactant, a builder and a stain removing amount of a composition according to claim 5. 
     
     
       27. A detergent composition according to claim 26, wherein said water soluble salt is present in an amount of form 0.5 to 20% by weight of the detergent composition. 
     
     
       28. A detergent composition according to claim 26 or claim 27 containing 5 to 60% builder and 20 to 75% water. 
     
     
       29. A water treatment composition comprising from 5 to 95% by weight thereof a composition according to claim 2, and from 5 to 90% by weight of the water treatment composition of at least one other water treatment agent selected from the group consisting of surfactants, sequestrants, chelating agents, corrosion inhibitors, scale inhibitors, biocides, bleaches, foam controlling agents, oxygen scavengers, pH controlling agents, buffers, dispersants and coagulants. 
     
     
       30. A method of manufacture of a composition according to claim 3 which comprises reacting vinylidene diphosphonic acid or a salt thereof with hypophosphorous acid or a salt thereof in aqueous solution in the presence of a source of free radicals. 
     
     
       31. A method of manufacture of a telomer which comprises reacting a water soluble compound according to claim 3 with more than 1 molar proportion of an unsaturated compound having an ethylenic or acetylenic bond activated by an adjacent sulphonate, phosphonate or carboxylate group, in aqueous solution in the presence of a free radical source.